Aromatic imidocarbonate composition and method of use for combatting fungi

ABSTRACT

Novel imidocarbonate derivatives having the formula:   wherein Y and Z, which may be the same or different, are individually an oxygen or sulfur atom; Ar is an unsubstituted or a halogen- or lower C1 - C4 alkyl (straight or branched)substituted benzene or pyridine nucleus, the number of the substituents being 1 to 3; R2 is a C1 - C18 alkyl (straight or branched), a C1 - C18 alkyl(straight or branched) having 1 to 3 hydroxy radicals or 1 to 3 alkoxycarbonyl (the alkoxy has 1 to 4 carbon atoms) radicals in the carbon chain, a C3 - C10 cycloalkyl, a C2 - C5 alkenyl (straight or branched), a C3 - C6 alkynyl (straight or branched), a phenylalkyl, the benzene nucleus of which may be unsubstituted or substituted by 1 to 4 halogen atoms, 1 to 4 lower C1 - C4 alkyl (straight or branched) radicals or a nitro radical, or a halogen- or lower C1 - C4 alkyl (straight or branched)-substituted phenoxyalkyl; R3 is a C1 - C18 alkyl (straight or branched) having 1 to 3 hydroxy radicals or 1 to 3 alkoxycarbonyl (the alkoxy has 1 to 4 carbon atoms) radicals in the carbon chain, a C2 - C5 alkenyl (straight or branched), a C3 - C6 alkynyl (straight or branched) or a phenylalkyl, the benzene nucleus of which may be unsubstituted or substituted by 1 to 4 halogen atoms, 1 to 4 lower C1 - C4 alkyl (straight or branched) radicals, a nitro radical or a C2 - C4 alkylene radical, provided that in case Ar is an unsubstituted or substituted benzene nucleus and R2 and R3 are phenylalkyl groups, the benzene nucleus of at least one of said phenylalkyl groups has a substituent, have strong microbicidal activities on a wide scope of microorganisms.

United States Patent 1 Tanaka et al.

[ Aug. 12, 1975 AROMATIC IMIDOCARBONATE COMPOSITION AND METHOD OF USE FOR COMBATTING FUNGI [75] Inventors: Shizuya Tanaka, Minoo; Toshiaki Ozaki; Akihiko Mine, both of Toyonaka; Katsutoshi Tanaka, Takarazuka; Sigeo Yamamoto, Toyonaka; Tadashi Ooishi, Takarazuka; Naganori Hino, Toyonaka; Takeo Satomi, Takarazuka, all of Japan [73] Assignee: Sumitomo Chemical Company,

Limited, Osaka, Japan [22] Filed: Jan. 31, 1974 [21] Appl. No.: 438,425

Related US. Application Data [60] Division of Ser. No. 238,537, March 27, l972, Pat. No. 3,832,351, which is a continuation-in-part of Ser. No. 133,744, April 13, 1971, abandoned.

[30] Foreign Application Priority Data Apr. 2l, 1970 Japan 45-34457 Nov. 22, 1971 Japan 4683874 [52] US. Cl. 424/263; 424/266; 424/301 [51] Int. Cl A0ln 9/22 [58] Field of Search 424/263 [56] References Cited OTHER PUBLICATIONS Haubein et al., J. Agr. Food Chem., Vol. 3, No. 6, pp. 55 557, Nov.Dec. (1965).

Ernst et al., Tetrahedron Letters, Pergamon Press, London, pp. 3023-3025.

Primary Examiner.lerome D. Goldberg Assistant ExaminerAllen J. Robinson Attorney, Agent, or Firm-Stevens, Davis, Miller & Mosher 5 7] ABSTRACT Novel imidocarbonate derivatives having the formula:

wherein Y and Z, which may be the same or different, are individually an oxygen or sulfur atom; Ar is an unsubstituted or a halogenor lower C, C, alkyl (straight or branched)-substituted benzene or pyridine nucleus, the number of the substituents being 1 to 3; R is a C, C alkyl (straight or branched), a C, C,,, alkyl(straight or branched) having 1 to 3 hydroxy radicals or 2 to 3 alkoxycarbonyl (the alkoxy has l to 4 carbon atoms) radicals in the carbon chain, a C C, cycloalkyl, a C C alkenyl (straight or branched), a C C alkynyl (straight or branched), a phenylalkyl, the benzene nucleus of which may be unsubstituted or substituted by l to 4 halogen atoms, l to 4 lower C, C, alkyl (straight or branched) radicals or a nitro radical, or a halogenor lower C, C alkyl (straight or branched)-substituted phenoxyalkyl; R is a C, C, alkyl (straight or branched) having I to 3 hydroxy radicals or 1 to 3 alkoxycarbonyl (the alkoxy has I to 4 carbon atoms) radicals in the carbon chain, a C C alkenyl (straight or branched), a C C alkynyl (straight or branched) or a phenylalkyl, the benzene nucleus of which may be unsubstituted or substituted by 1 to 4 halogen atoms, 1 to 4 lower C, C, alkyl (straight or branched) radicals, a nitro radical or a C C alkylene radical, provided that in case Ar is an unsubstituted or substituted benzene nucleus and R and R are phenylalkyl groups, the benzene nucleus of at least one of said phenylalkyl groups has a substituent, have strong microbicidal activities on a wide scope of microorganisms.

4 Claims, No Drawings AROMATIC IMIDOCARBONATE COMPOSITION AND METHOD OF USE FOR COMBATTING FUNGH CROSS-REFERENCES TO OTHER APPLICATIONS wherein Y and Z, which may be the same or different,

, are individually an oxygen or sulfur atom; Ar is an un substituted or halogenor lower C C alkyl (stragith or branched)-substituted benzene nucleus or an unsubstituted or halogenor lower C C, alkyl (straight or branched)-substituted pyridine nucleus, the number of the substituents being 1 to 3; R is a C C alkyl A straight or branched), a C C alkyl (straight or branched) having 1 to 3 hydroxy radicals or 1 to 3 alkoxycarbonyl (the alkoxy has 1 to 4 carbon atoms) radicals in the carbon chain, a C;,-C cycloalkyl, a C C alkenyl (straight or branched), a C C alkynyl (straight or branched), a phenylalkyl, the benzene nucleus of which may be unsubstituted or substituted by l to 4 halogen atoms, 1 to 4 lower C -C alkyl (straight or branched) radicals or a nitro radical, or a halogenor lower C C alkyl (straight or branched)- substituted phenoxyalkyl; R is a C C alkyl (straight or branched) having 1 to 3 hydroxy radicals or 1 to 3 alkoxycarbonyl (the alkoxy has 1 to 4 carbon atoms) radicals in the carbon chain, a C C alkenyl (straight or branched), a C C alkynyl (straight or branched) or a phenylalkyl, the benzene nucleus of which may be unsubstituted or substituted by l to 4 halogen atoms, 1 to 4 lower C C alkyl (straight or branched) radicals, 2 nitro radical or C C, alkylene radical, provided that in case Ar is an unsubstituted or substituted benzene nucleus and R and R are phenylalkyl groups, the benzene nucleus of at least one of said phenylalkyl groups has a substituent; processes for preparing said compounds; and non-medical microbicides containing said compounds as active ingredients.

A preferred imidocarbonate derivative is represented by the formula:

wherein Y is the same as defined above and R is a C C alkyl (straight or branched), a C C cycloalkyl or a lower C C alkyl (straight or branched)- substituted benzyl radical.

in the definitions of Ar, R R and R, examples of the lower alkyl are preferably methyl, ethyl, propyl, isopropyl, isobutyl, n-butyl, t-butyl, etc.; examples of the alkenyl are vinyl, allyl, crotyl, butenyl, etc.; examples of the alkynyl are preferably propagyl, etc.; examples of phenylalkyl are preferably benzyl, phenetyl, a-methyl benzyl, phenylpropyl, etc.; examples of the halogen are chlorine, bromine, fluorine and iodine, examples of the alkoxycarbonyl are preferably methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, etc.; and

examples of the cycloalkyl are preferably cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclopentyl, etc.

The above-mentioned imidocarbonate derivatives are synthesized by the following processes:

Synthesis process (A) A thionocarbamic or dithiocarbamic acid ester derivative represented by the general formula (11):

wherein Ar, R and Y are the same as defined above, is reacted with an organic halide represented by the general formula (III):

(Ill) wherein R is the same as defined above; and X is a hal ogen atom.

Synthesis process (B) An isocyanic acid dichloride derivative represented by the general formula (IV):

wherein Ar is the same as defined above, is reacted with an alkali metal alcoholate or mercaptide derivative represented by the general formula (V):

R Y M wherein R and Y are the same as defined above; and M is an alkali metal atom.

Synthesis process (C) An imidocarbonate chloride derivative represented by the general formula (VI):

wherein Ar and R are the same as defined above, is reacted with an alkali metal alcoholate or mercaptide derivative represented by the general formula (Vll):

R Z M vii) wherein R", Z and M are the same as defined above.

Synthesis process (D) A dialkali metal imidodithiocarbonate derivative represented by the general formula (VIII):

(VIII) wherein Ar and M are the same as defined above, is reacted with an organic halide represented by the general formula (IX):

wherein R and X are the same as defined above.

Several imidocarbonate, imidomonothiocarbonate and imidodithiocarbonate derivatives have been well known hitherto. However, all the compounds of the present invention are novel, and the present inventors have found, as the result of extensive studies, that these compounds have strong microbicidal effects on an extremely wide scope of microorganisms. They have prominent effects on such a wide scope of microorganisms as rice blast (Pyriculariu oryzae), helminthosporium leaf spot (Coc'lzliobolus miyabeanus), sheath blight (Pellicularia sasakii), bacterial leaf blight (Xan- Ilmhwnas oryzue), and the like pathogens of rice plants, and sclerotinia rot (Sclerorinia sclerotiorum), brown rot (Sclerotinia fructigena), gray mold (Botrytis c'inerea), cork spot (Alternaria mali), blossom blight (Sclerotiniu mali), powdery mildew (Erysiplze c'iclloraceurum), alternaria leaf spot (Alter-"aria brassicae), damping-off (Pythium debaryanum), bacterial Canker (Corynebacterium michigunense), ripe rot (Glumerella cingulata), southern blight (Corticium roljlrii) and the like pathogens of agricultural and horticultural crops, and are markedly excellent plant disease-controlling chemicals capable of controlling two or more kinds of plant diseases at the same time. Further, the present compounds are effective for the control of molds propagating in industrial products and hence are excellent as industrial microbicides and also have herbicidal activities. Moreover, they are extremely low in toxicity and scarcely have detrimental actions on mammals and fishes.

The synthesis process (A) is carried out in such a manner that to a solution of 1 mole of the said thionocarbamic or dithiocarbamic acid ester derivative (II) in methanol, ethanol, tetrahydrofuran, dioxane, DMSO or DMF are added 1 to 2 moles of the halide (III) and l to 1.5 moles ofa base (e.g., a hydroxide of an alkali or alkaline earth metal such as NaOI-I, KOH or Ca(OH) or an alkali metal alcoholate such as NaOCH NaOC I-I or KOCH, or tertiary amines such as triethylamine, pyridine or N,N-dimethylaniline) for neutralizing the hydrohalic acid which is formed at the time of reaction, and the resulting mixture is reacted. In this case, there may be adopted either the procedure that the base is first added to the solution of carbamic acid ester derivative and then the organic halide is added, or the procedurethat the organic halide is first added to the solution of carbamic acid ester derivative and then the base is added. The-reaction is effected by stirring the resulting mixture at such a mild temperature condition as at 0 to 100C for l to 4 hours. After completion of the reaction, the reaction mixture is poured into an excess amount of water, and the resulting crystal or oil layer is separated by filtration or by extraction with a water-immiscible organic solvent such as benzene, toluene, ethyl acetate, ether or the like.

The synthesis process (B) is carried out in such a manner that a solution or suspension of 2 to 3 moles of the alkali metal alcoholate or mercaptide derivative (V) in an alcohol such as methanol or ethanol, an ether such as ether, dioxane or tetrahydrofuran, or a hydrocarbon such as benzene or toluene is mixed with 1 mole of the isocyanic acid dichloride derivative (IV), and the resulting mixture is reacted to obtain a desired product. The reaction may be effected at any temperature within the range of lOC to 100C. Since the reaction is exothermic, the starting materials are ordinarily mixed at a temperature on the lower side of lO to 40C and the resulting mixture is maintained at said temperature for 3 to 4 hours, or maintained at 40 to 100C for l to 2 hours. An alkali metal salt formed during the reaction is separated by filtration or by dissolution in water, and then the oil layer is extracted with a water-immiscible organic solvent, whereby the product can be isolated. The product may be further purified by distillation or recrystallization.

The synthesis process (C) characteristically differs from the synthesis process (B) in that l to 1.5 moles of the alkali metal alcoholate or mercaptide derivative (VII) per mole of the imidocarbonate chloride derivative (VI) is used to make it possible to optionally obtain, by selection of reaction reagents, a compound of the general formula (I), in which Y and Z or R and R are the same as or different from each other. The reaction temperature and time and the treatment, after operations, are the same as in the synthesis process (B).

The snythesis process (D) is carried out in such a manner that 1 mole of the dialkali metal imidodithiocarbonate (VIII) is reacted with 2 to 3 moles ofthegorganic halide (IX), whereby a desired product can be obtained. The reaction solvent may be selected from the group consisting of water, alcohol, acetone, DMF, dioxane, tetrahydrofuran, etc., and a mixture thereof. It is, of course, possible to use the dialkali rn'etal imidodithiocarbonate (VIII) in an isolated form. It is also possible that 1 mole of the starting amine, 1 mole of carbon disulfide and 2 moles of an alkali metal hydroxide are mixed in the above-mentioned reaction solvent, and the resulting mixture is reacted as it is, i.e. without isolation, with the organic halide (IX). In case a chloride, which is low in reactivity, is used as the organic halide, it is of course possible to carry out the re- I action in the presence of such a catalyst as sodium bromide, potassium bromide, sodium iodide, potassium iodide, or pyridine, triethylamine or the like. The reaction may be effected at a temperature within the range of 0 to 100C, preferably 0 to 70C. Ordinarily, the reaction terminates within 1 to 4 hours. After the reaction, the reaction mixture is poured into water to dissolve the formed alkali metal halide, and the resulting crystal or oily substance is recovered by filtration or extraction to obtain a desired product.

In actual application, the thus obtained compounds of the present invention may be applied as they are or may be formulated into any of such preparations as granules, dusts, wettable powders and emulsifiable concentrates. It is desirable thatthese, preparations are suitably used according to the kinds and sizes of crops and to application purposes. 1 2 t In formulating thesejpreparations, there. may beused such solid carriers as talc, bentonite,-clay,:l aolin, diatomaceous earth, vermiculite slaked lime, etcy.-;- such liquid carriers as benzene, alcohols,.aceton 'e, xylene, diox- V ane, methyl naphthalene,- c yclohexanone,-j-etc.;. and such surfactants (wetting agents andemulsifiers and the like) andbinders, as alkyl sulfates; alkyl sulfonates,

" aryl sulfonates, polyethylene glycol ethers, polyhydrie alcohol esters, polyoxyethylene alkylphenylphenol ether, ligninsulfonic acidalkali metal salt, alkylbenzenesulfonic acid alkali metal salt, polyvinyl alcohol, etc. In application, these preparations may'no't only. be used in admixture with agricultural surface active agents such as spreaders and the like to expect the en hancement and accuracy of the effectiveness thereof, but also be used in admixture with such agricultural chemicals as fungicides, insecticides, nematocides, herbicides f ete, and with fertilizers. l

The present invention is illustrated 111 further detailwith reference to examples, but it isneedlessto say that the kindsof starting materials used' fo r preparation of the p reserit compounds; the reaction conditions, and the'ltinds and mixing proportions of additives for the present compounds are variable over wide scopes without being limited only to those set forth in theexarnmethylthionocarbamate. Into this solution was dropped at to C 16.1 g (0.1 mole) of p-chlorobenzyl chloride, and the resulting mixture was stirred at said temperature for 2 hours. Subsequently, the reaction EXAMPLE 2 Synthesis process (B):

Synthesis of N-2,5-dichlorophenyl-0,0'-di( aethoxycarbonylethyl) imidocarbonate (Compound No. 63): i

Into a suspension of 30.8 g (0.22 mole) of sodium salt of ethyl a-hydroxypropionate in 300 ml of dry ether was dropped 24.3 g (0.1 mole) of 2,5-dichlorophenyl isocyanic acid dichloride with stirring and with cooling "chlorobenzylimidodithiocarbonate di(a ethoxycarbonylethyl) imidocarbonate, yield 8 7 EXAMPLE 3 Synthesis process (C):

- Synthesis of N-3-pyridyl-O-butyl-S-3,4- dichlorobenzyl imidothiocarbonate (Compound No.

Into a solution of 0.12 mole of sodium 3,4dichlorobenzyl mercaptide in 200 ml of methanol was dropped .with stirring at 0 to 5C over a period of 1 hour 21.2

g (0.1 mole) of N-3-pyridyl-O-butylimidocarbonate chloride, and .the resulting mixture was allowed to stand at room temperature for 3 hours. Subsequently, the reaction mixture was poured into 650 ml of water, and then extracted with 200 ml of benzene. Subse gquently, the-benzene layer was washed once with water and dried with anhydrous magnesiumsulfate, and then -the-benzene was removed by evaporation to obtain 30.1 g of the desired compound in an oily form.

" EXAMPLE ij'j' Synthesis process (D):

of N-:3pyridyl-S.S'-di-2 (Compound No.

Synthesis To a solution of 1 1.2 g (0.2 mole) of caustic potash in arni'xed solvent comprising 60 ml of'ethanol and 20 m1 of water was added 9.4 g (0.1 mole) of 3- aminopyridine. To the resulting mixture was added 7.6

g (0.1 mole) of carbon disulfide at 10 to 20C with stirring over a period of 1.5 hours. After allowing to stand at room temperature for 2 hours, the mixture was cooled to 5 to 15C, and then 35.4 g (0.22 mole) of 2- chlorobenzyl chloride was dropped into the reaction mixture over a period of 1.5 hours. Thereafter, the reaction mixture was poured into 200 ml of water, and an oil layer formed was extracted with ethyl acetate, and the extracts were washed once with water and then dried with anhydrous sodium sulfate. Subsequently. the solvent was removed by distillation under reduced pressure to obtain 35.5 g of N-3-pyridyl-S,S-di'2- chlorobenzyl-imidodithiocarbonate, yield EXAMPLE 5 Synthesis of N-3-pyridyl-S-n-butyl-S'-p-tbutylbenzyl-imidodithiocarbonate (Compound No. 84):

In ml of methanol was dissolved 2.3 g (0.1 mole) of metallic sodium and 31.6 g (0.1 mole) of p-t-butylbenzyl-N-3'pyridyl dithiocarbamate was then added to the resulting solution at 15C to dissolve it in the solution. Into the thus obtained solution was dropped at 15.- 20C 15.1 g (0.11 mole) of n-butyl bromide (n-C H Br). The resulting mixture was maintained at said temperature for 2 hrs. and then at 40C for 1 hr. The resultingreactionmixture was poured into 400 ml. of iced water, and the separated oil material was extracted with 200 ml of ethyl acetate. The thus obtained ethyl acetate layer was once washed with 200 m1 of water, dried with anhydrous sodium sulfate and then subjected to distillation under reducedpressure to obtain 33.1 g (yield: 89 ofa pale yellow. oily material.

EXAMPLE 6 in 100 ml of methanol was dissolved 5.6 g (0.1 mole) Synthesis of py y y p of potassium hydroxide, and 25.1 g (0.1 mole) of 4- butylbenzyl-imidothiocarbonate (Compound No. 96): methycyciohexyl N 3 pyndyl thlqnocafliamate.

. then added thereto at 15C to obtain a umfonn liquid,

In 70 ml of methanol was dissolved 4.4 g (0.1 1 mole) into which 27 7 g (0 1 mole) of p y y ofsodium hydroxide, and 21 g (0.1 mole) of n-butyl-N- 10 mide was pp' at The resulting 3-pyridy1thionocarbamate was then dissolved therein at mixture was maintained at for and then 20C. To the resulting solution was added dropwise 400 ml of iced water The resumn Se 22.7 g 0.1 mole) of t-butylbenzyl bromide at 20 g p 25C. The resulting mixture was maintained at said rated Olly material was.extrac.tcd with 200 m] of ethyl temperature for 1 5 hrs after which the reaction mix- 15 F The h g 1 layer was once washed turewas poured into ml of iced water and subwith i dried i hydrous Sodmm Sulfate and jected to extraction with 200 ml of ethyl acetate. The then.sub'lected distillation under mduced pr?ssure to resulting ethyl acetate layer was treated in the same (imam g (yield: Ofa pale yellow Olly matemanner as in Example 5 to obtain an oil, which was solidified after being allowed to stand at room tempera- 20 ture over night. EXAMPLE 9 EXAMPLE 7 Synthesis of N-3-pyridy1-S-cyclohexyl-S-p-t- Synthesis of N-3-pyridy1-S,S'-di-p-t-buty1benzy1- buty1benzyl-imidodithiocarbonate (Compound No. imidodithiocarbonate (Compound No. 1 18): 25 112):

To 100 ml of ethanol containing dissolved therein 5.6 At 10C, 31.6 g (O.1 mole) of p-t-buty1benzyl-N-3- g (0.1 mole) of potassium hydroxide was added 31 .6 g pyridyldithiocarbamate was added to a sodium methylof p-t-butylbenzyl-N-3-pyridyl dithiocarbamate, and ate solution prepared by dissolving 2.3 g of metallic sothe resulting mix re wa m in in at to hi h dium in 100 m1 of methanol. to obtain a solution. At the 20 g 1 o e) f p-t-butylbenzyl chloride was added same temperature. 23.1 g (0.1 1 mole) of cyclohcxyl iodropwise in 30 min. The resulting mixture was maindide was added to said solution, and the resulting mixtained at 20C for 1.5 hrs. and then poured into 200 m1 ture was maintained at 30C for 1 hr. and then at C of iced water. The resulting oil layer was treated in the for 2 hrs. The resulting reaction mixture was then same manner as in Example 5 to Obtain 43 g O a pa e poured into 400 ml of iced water and then subjected to yellow oily material. To this oily material was added 30 35 the same treatment as in Example 8 to obtain 23.3 g ml of n-hexane and the resulting mixture was allowed (yield:: 71 of a yellow oily material. to stand in a refregerator over night to obtain 34.6 g Physical constants and elementary analysis values of. (yield: 75 of a crystal having a melting point of 77 compound synthesized according to the processes of 80C. 40 the present invention are as set forth in Table 1.

Table 1 EXAMPLE 8 Synthesis of N-3-pyridy1-O-4-methylcyclohexyl-S-pt-butyl-benzylimidothiocarbonate (Compound No. 107):

('mu- Slructural formula Physical Elementary analysis value (71 1 pound constant No. C H N S (1 Br SCH 3 1 1| 'N=C\ n,. (a! d 54.42 4.25 0.07 20.76 HAN N SCH c] I 53 54.02 4.02 8.90 20.42 11.14

g@ Found sc u E TN=C r q; 71) 4 i e t t 11,. a t 8.6 1 L80 ll). )8 N SCH -C1 1mm] 55.5: 4.71 so; mm 111s Found CH /S-C Loj-"= u,,"" (am 55.4) us so: 1913 nm N Low} 55.42 4.95 8.16 19.01 111.5

Found 

1. A FUNGICIDAL COMPOSITION COMPRISING AS THE ACTIVE INGREDIENT A FUNGICIDALLY EFFECTIVE AMOUNT OF AN IMIDOCARBONATE DERIVATIVE REPRESENTED BY THE FORMULA, AR-N=C(-Y-R2)-Z-R3 WHEREIN Y AND Z, WHICH MAY BE THE SAME OR DIFFERENT, ARE INDIVIDUALLY AN OXYGEN OR SULFUR ATOM, AR IS AN UNSUBSTITUTED OR A HALOGEN-OR LOWER C1-C4 ALKYYL(STRAIGHT OR BRACHED)-SUBSTITUTED PYRIDINE NUCLEUS, THE NUMBER OF THE SUBSTITUENTS BEING 1 TO 3, R2 IS A C1-C18 STRAIGHT ALKYL, A C1-C6 BRANCHED ALKYL, A C1-C3 ALKYL(STRAIGHT OR BRANCHED) HAVING 1 TO 2 HYDROXY RADICALS PROVIDED THAT 2 HYDROXY GROUPS ARE NOT BONDED TO THE SAME CARBON ATOM OR ONE ALKOXY CARBONYL (THE ALKOXY HAS 1 TO 4 CARBON ATOMS) RADICAL IN THE CARBON CHAIN, A CYCLOAKYL HAVING UP TO 6 CARBON ATOMS, ALLYL, PROPARGYL, A BENZYL, THE BENZENE NUCLEUS OF WHICH MAY BE UNSUBSTITUTED OR SUBSTITUTED BY 1 TO 4 HALOGEN ATOMS, 1 TO 4 LOWER C1-C4 ALKYL(STRAIGHT OR BRANCHED) RADICALS OR A NITRO RADICAL, OR A HALOGEN- OR LOWER C1-C4 ALKYL (STRAIGHT OR BRANCHED)-SUBSTITUTED PHENOXY-C1-C2 ALKYL, AND R3 IS A C1-C3 ALKYL(STRAIGHT OR BRANCHED) HAVING 1 TO 2 HYDROXY RADICALS OR ONE ALKOXYCARBONYL ( THE ALKOXY HAS 1 TO 4 CARBON ATOMS) RADICAL IN THE CARBON CHAIN, ALLYL, PROPARGYL, OR A BENZYL, THE BENZENE NUCLEUS OF WHICH MAY BE UNSUBSTITUTED OR SUBSTITUTED BY 1 TO 4 HALOGEN ATOMS, 1 TO 4 LOWER C1-C4 ALKYL ALKYL(STRAIGHT OR BRANCHED) RADICALS, A NITRO RADI CAL OR A C2-C4 ALKYLENE RADICAL AND AN INERT CARRIER
 2. A method for combatting phytopathogenic fungi on plants comprising applying to said fungi a fungicidally effective amount of the imidocarbonate compound of claim
 1. 3. The method of claim 2, wherein said compound is represented by the formula,
 4. The method of claim 2, wherein said fungi is powdery mildew. 